Composition for increasing the adhesive power of bitumens and tars



Patented Sept. 2Q, 1949 Tao srArEs PATENT OFFICE COMPOSITION FOR INCREASING THE A D- :xHESI VEzPOWER OF BITUMENSAND...TARS

fRobertD upas, Clichy, France, ass'ignor to'Stan'darid Oil "Development Company, New Yoi-k,

N;Y.; a corporate body zNo lDrawingh Appl icatlon'March 12,1947, Serial 1N0, 734,234. .In France June 21, 1941 "-s'ectionl, PubIicLawIB90,Augustr8, 1946 Pat'entexpires J1me u't-luflififil .TIfhezpresent invention :relates to'r-the'timprove- I ment of the adhesive power of bituminousrhindrlars, coalitar, shale tar :anda the :liket-to materials iiin'rgeneralgandimoreiparticularly to road making materials.

s. It is known thatalthough-hydrocarbon binders 'such as bitumen, tar, -and the i like "adhere 1 satis- *iactorilyi to dry materials; they only adhere :with difliculty to damp nnaterials particularly if such materials are acid, such -as' flint,*quartzite, and the like.

' It is therefore" necessaryprierabl to' work in fine weather, since ifa-shower' of rain "occursimm'ediatly -after the formation-ofthe surface =-it The amine basesproposed inthis lattenFrench "patent are amine bases of high 'molecular weight having a long aliphatic :chainysuch bases are at present very rare on the market and difficult to procure.

- The applicant -has-observed that *p'olyvalent amino bases of which some have been mentioned metal salts which are soluble in water produce practically no improvement in the adhesiveness of the binders when they are mixed alone with said binders in small proportions, but that on the other hand such salts produce a substantial, improvement when they are in the presence of organic bases of high molecuar weight which are capable of forming complexes of association. Very often such organic bases have a certain comparatively small natural activity which can be increased tenfold by the formation of a complex of association with a polyvalent metal salt such for example as zinc chloride. Now, it is well known that such complexes are readily formed in an aqueous medium. In order to prepare these complexes, to an aqueous colloidal dispersion of a chlorhydrate of organic bases of high molecular weight is added a solution of a polyvalent metal salt. It has been found that the best results obtained with polyvalent metal chlorides such as e'lzfllaims. ((31.106-281) a .32 zinc i chloiiide,.,;ferr'ic a chloride, .and ;the .Jike. 'iIn ithisa-manner complexes. comprising. amino .bases and -a polyvalen'tmetal chlorideare -.obtained.in the-.iiorm ofia precipitate, whichis separated from the mother,.l-iquor,.-and such complexes may con- -.-tain from al toa3 molecules lot polyvalent inetal schloridexto threemolecules of. .amine hydrochlorideuofhighmolecularweight.

..By way.,of example, thefollowing complexes 1 .have beeniprepared:

*rMethylenerbhre :hydroch'lorldezinc rclsiloride Rhodamine:rhydrochlorfdwaluminum chloride a more or less completely washesthe material 25 *"Malachitemdmcmofldwferrici'ichlonde In general, the amino bases which "are most suitableiorthe formation 'of'such complexes'are -amin0' bases of'hi'gh molecular'wight containing several aromatic "nuclei 'but me lon aliphatic chains, and which produce colloldal dispersions 'in 'water, such 'as basic dyes, -methy1eneblue,

malachite green. rhoda-m'ines, --rosam'ines, aura "mines,-"and the like.

With *regard to the amines -0f"high' molecular "weih't having long aliphatic chains, such asheptadecylaminel heptad'ecylpyrid ne, the hydrochlo Tides -of which *are or substantially insoluble they are not capab e of forming such advantageous complexes, :such organic bases moreover already 0 shave a particularlyzhixh natural :fiCtiVity shout ten times higher than that of leadeoleate'), :wh ereas the :amin'orbases containing several: .aro- -mat c nuclei J01! whiche'there areronly :assma'll *number o'f very :s'hont'ss'ide ichains su'chias -.:those provement is observed by using one of the components of the complex separately.

The amines with several aromatic nuclei without long aliphatic chains, which are proposed by the present invention, in association with a polyvalent metal chloride, are much less rare than the amino bases proposed in French Patent No. 847,829 and are commonly found on the market.

The present invention therefore has for its object to add to the binders small percentages of the complexes hereinbefore mentioned in order to imtively small quantity of fluid bitumen or tar con-1 taining a higher proportion of complex and then The examples which are given above in order to make the invention more clearly understood are in no way limitative. All the complexes ob tained byprecipitation' of an amino salt and a polyvalent metal salt: iron, manganese, zinc, copper, aluminum, lead, and so forth, produce similar results.

add the remainder of the binder in the usual.

form: fluid bitumen. tar, bitumen or tar emulsion. accord ng to the pre-coating method de-v scribed in' French Patents Nos. 826,789 and 847,829. In this case. the pre-coating binder may contain from 1 to 5 or even 10% and more of one of said complexes. a I

The following laboratory tests have'been adopted in order to determine the improvement produced in the adhesive power by adding the above-mentioned complexes: 7

1. Process without pre-coating.Comparison has been made of a cut-back .(fiuidbitumen) prepared with 40% of kerosene andf60%fof asnhalt h in a ne a on f 189-290 a 2 94C- and containing 1% by ,weightoi lead oleate. with a cut-back of the same naturebut in which the lead oleate had been replaced by a complex comprising an amine and a polyvalent ;metal salt. for example the complex comprising methylene blue hydrochloride andzine chloride.

Having introduced gm of gravel (1.2 to .4 mm.) into a test tube containing 50 gm. of water and 5 gm. of cut-back to be compared; agitation was efiected for 30 seconds in a shakingmachine. By using the methylene blue hydrochloridezinc chloride complexin a. proportion of 0.1%,

the gravel was coated .in just as satisfactory a manner-in the presenceof water as in the case of the cut-back containing 1% of lead oleate.

2. Process with pre-coating.150 gm. of moist.

plex.

I claim:

1.' A bituminous composition of improved adhesive power which consists essentially of a bitumen having incorporated therein'from 0.1 to 10% of: a complex compound of a polyvalent metal chloride and an organic dyestufi containing 'a'ba sic group selected from the group consisting oimethylene blue hydrochloride, rhodamine.v hydrochloride and malachite green hydrochloride."

2. A composition according to claim 1 in which the polyvalent metal chloride is zinc chloride.

3. The .composition defined by claim 1 in, which the polyvalent metal chloride is aluminum chloride. 1 c r .4.

4. The composition defined by claim 1 in which the'polyvalent metal chloride is ferric chloride. Y v 5. A bituminous composition'of improved adhesive power consisting essentially of a bitumen containing from 0.1'to 10% of a complex consisting of methylene blue hydrochlorideand' 'a polyvalent metal chloride. 1

6. A bituminous composition of improved'adhesive power consisting essentially of a bitumen containing from 0.1 to 10% of a complex consisting of malachite green hydrochloride and a polyvalent metal chloride. Y 1

7. A bituminous composition of improved-adhesive power consisting essentially of a bitumen containing from 0.1 to 10% of a complex consisting of rhodamine hydrochloride and a-polyvalent metal chloride.

-ROBERT bums.

REFERENCES CITED 1 The following references are of record in the file of this patent:-

UNITED STATES PATENTS Number Name 7 Date 1,772,522 Rodd et a1. Aug. 12, 1930 2,191,295 Dohse Feb. 20, 1940 V FOREIGN PATENTS Number Country Date 7 France July 10, 1939 

